Powdered resins with fillers

ABSTRACT

Particulate binder compositions and methods for making and using same are provided. The binder composition for producing composite lignocellulose products can include an aldehyde based resin and a filler, an extender, or a combination thereof. The binder composition can be in the form of particulates. The particulates can each comprises the filler, the extender, or the combination thereof and the aldehyde based resin.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of co-pending U.S. patent applicationSer. No. 13/627,307, filed on Sep. 26, 2012, which claims priority toU.S. Provisional Patent Application No. 61/541,508, filed on Sep. 30,2011, which are both incorporated by reference herein.

BACKGROUND

Field

Embodiments described herein generally relate to particulate bindercompositions for use in making composite products. More particularly,such embodiments relate to particulate binder compositions containingfillers and/or extenders for use in making lignocellulose-containingcomposite products.

Description of the Related Art

Powdered or particulate, curable aldehyde based resins, e.g.,phenol-formaldehyde resole resins, have found wide use as an adhesivefor a variety of lignocellulose composite products such as orientedstrand board (OSB) and other similar wafer or chip board products.Phenol-formaldehyde resole resins are typically prepared by reacting amolar excess of formaldehyde with phenol under liquid, e.g., aqueous,alkaline reaction conditions. The resulting liquid phenol-formaldehyderesole resin is then spray-dried to produce the curablephenol-formaldehyde resin powder that is used as an adhesive.

Typical spray-dried phenol-formaldehyde resin powders producelignocellulose products, e.g., oriented strand board, that meet orexceed desired physical properties, e.g., internal bond strength. Theamount of spray-dried phenol-formaldehyde resin powder typicallyrequired to produce lignocellulose products having the desired physicalproperties, however, adds to the costs associated with producinglignocellulose composite products.

There is a need, therefore, for improved binder compositions forproducing composite products, e.g., lignocellulose-containing compositeproducts, and methods for making and using the same.

SUMMARY

Particulate binder compositions and methods for making and using sameare provided. In one or more embodiments, a binder composition forproducing composite lignocellulose products can include an aldehydebased resin and a filler, an extender, or a combination thereof. Thebinder composition can be in the form of particulates. The particulatescan each comprises the filler, the extender, or the combination thereofand the aldehyde based resin.

In one or more embodiments, a method for producing a binder compositioncan include combining a filler, an extender, or a both with an aldehydebased resin in the presence of a liquid medium to produce a mixture. Atleast a portion of the liquid medium can be removed to produce aparticulate binder composition, wherein each particulate comprises thefiller, the extender, or the combination thereof and the aldehyde basedresin.

In one or more embodiments, a method for producing a binder compositioncan include spray-drying an aerated liquid mixture that includes afiller, an extender, or a combination thereof and an aldehyde basedresin to produce a spray-dried binder composition. The spray-driedbinder composition can be in the form of particulates. Each particulatecan include the filler, the extender, or the combination thereof and thealdehyde based resin.

In one or more embodiments, a composite product can include a pluralityof lignocellulose substrates and an at least partially cured bindercomposition. The binder composition, prior to at least partial curing,can include an aldehyde based resin and a filler, an extender, or acombination thereof. The binder composition can be in the form ofparticulates. Each particulate can include the filler, the extender, orthe combination thereof and the aldehyde based resin.

In one or more embodiments, a method for producing a particulate bindercomposition can include synthesizing a liquid phenol-formaldehyde resoleresin. A filler, an extender, or both can be combined with the liquidphenol-formaldehyde resole resin in an amount sufficient to produce amixture containing about 1 wt % to about 25 wt % of the filler, theextender, or both, based on the combined weight of the liquidphenol-formaldehyde resole resin solids and the filler, the extender, orboth. The mixture can be agitated to produce an aerated mixture. Theaerated mixture can be spray-dried to produce a spray-dried particulatebinder composition, wherein each particulate comprises the filler, theextender, or the combination thereof and the aldehyde based resin.

In one or more embodiments, a method for making a composite product caninclude contacting a plurality of lignocellulose substrates with aparticulate binder composition. The particulate binder composition caninclude an aldehyde based resin; and a filler, an extender, or acombination thereof. Each particulate can include the filler, theextender, or the combination thereof and the aldehyde based resin. Thebinder composition can be at least partially cured to produce acomposite product.

In one or more embodiments, a binder composition for producing compositelignocellulose products can include mixture of a first plurality ofparticulates and second plurality of particulates. The first pluralityof particulates can include one or more aldehyde based resins. Thesecond plurality of particulates can include one or more fillers, one ormore extenders, or a combination thereof.

In one or more embodiments, a method for producing a binder compositioncan include removing at least a portion of a liquid medium combined withan aldehyde based resin to produce a first plurality of particulates.The method can also include combining the first plurality ofparticulates with a second plurality of particulates to produce a bindercomposition. The second plurality of particulates can include one ormore fillers, one or more extenders, or a combination thereof.

In one or more embodiments, a method for producing a binder composition,can include spray-drying an aerated liquid mixture that includes one ormore aldehyde based resins to produce a first plurality of particulates.The method can also include combining the first plurality ofparticulates with a second plurality of particulates to produce a bindercomposition. The second plurality of particulates can include one ormore fillers, one or more extenders, or a combination thereof.

In one or more embodiments, a composite product can include a pluralityof lignocellulose substrates and an at least partially cured bindercomposition. The binder composition, prior to at least partial curing,can include a mixture of a first plurality of particulates and a secondplurality of particulates. The first plurality of particulates caninclude one or more aldehyde based resins. The second plurality ofparticulates can include one or more fillers, one or more extenders, ora combination thereof.

In one or more embodiments, a method for producing a particulate bindercomposition can include synthesizing a liquid phenol-formaldehyde resoleresin. The liquid phenol-formaldehyde resin can be agitated to producean aerated phenol-formaldehyde resole resin. The method can also includespray-drying the aerated phenol-formaldehyde resole resin to produce aspray-dried particulate phenol-formaldehyde resole resin. Thespray-dried particulate phenol-formaldehyde resole resin can be combinedwith one or more fillers, one or more extenders or a combination thereofto produce a binder composition. The one or more fillers, the one ormore extenders, or the combination thereof can be in particulate form.

In one or more embodiments, a method for making a composite product caninclude contacting a plurality of lignocellulose substrates with aparticulate binder composition. The particulate binder composition caninclude a mixture of a first plurality of particulates and a secondplurality of particulates. The first plurality of particulates caninclude one or more aldehyde based resins. The second plurality ofparticulates can include one or more fillers, one or more extenders, ora combination thereof. The method can also include at least partiallycuring the binder composition to produce a composite product.

DETAILED DESCRIPTION

The particulate binder composition can include one or more aldehydebased resins and one or more fillers and/or one or more extenders. Inone or more embodiments, the discrete or individual particulates of thebinder composition can include the aldehyde based resin and the fillerand/or extender. In one or more embodiments, the discrete or individualparticulates of the binder composition can be either the aldehyde basedresin, the filler, or the extender. Said another way, the bindercomposition can include a mixture of a first plurality of particulatesthat include the aldehyde based resin and a second plurality ofparticulates that include the filler, the extender, or a combination ofthe filler and extender. The first plurality of particulates can be freefrom any intentionally added filler and/or extender. The secondplurality can be free from any intentionally added aldehyde based resin.The particulate binder composition that includes the aldehyde basedresin and the filler and/or extender can be used to produce alignocellulose-containing composite product or “composite product” thatmeets certain physical property requirements while requiring lessaldehyde based resin as compared to a comparativelignocellulose-containing composite product or “comparative compositeproduct” having the same aldehyde based resin, but no filler orextender.

For example, the composite product produced with the particulate bindercomposition having the aldehyde based resin and the fillers and/orextender can include about 1%, about 3%, about 5%, about 7%, about 8%,about 10%, about 12%, about 14%, about 16%, about 18%, about 20%, about22%, about 24%, or about 26% less aldehyde based resin as compared tothe amount of aldehyde based resin present in the comparative compositeproduct. In another example, the presence of the one or more fillersand/or extenders in the particulate binder composition can be used toproduce a composite product that contains from about 1% to about 25%,about 5% to about 20%, about 5% to about 18%, or about 7% to about 15%less aldehyde based resin as compared to the amount of aldehyde basedresin present in the comparative composite product. In another example,the amount of aldehyde based resin in the composite product producedwith the binder composition that includes the aldehyde based resin andthe one or more fillers and/or extenders can be reduced by an amountranging from a low of about 1%, about 3%, about 6%, or about 8% to ahigh of about 14%, about 16%, about 18%, about 20%, about 22%, about24%, or about 26% relative to the amount of the aldehyde based resinpresent in the comparative composite product, with suitable rangesincluding the combination of any two values.

One or more properties of the composite product that can remain aboutthe same and/or improve when produced with the particulate bindercomposition that includes the aldehyde based resin and the filler and/orextender, as compared to the comparative composite product, can include,but is not limited to, internal bond strength (IB), bond durability,e.g., boiled internal bond “BIB,” water absorption, thickness swell, andbending, e.g., modulus of rupture “MOR,” modulus of elasticity “MOE,”maximum moment “MM,” and modulus of inertia “EI.” For example, theinternal bond strength of a composite product produced with theparticulate binder composition that includes the aldehyde based resinand the one or more fillers and/or extenders can be equal to or greaterthan the internal bond strength of the comparative product.

Processes for producing the particulate binder composition, such asspray-drying, freeze drying, vacuum drying, precipitation, air drying,and dry spinning a liquid mixture that includes the aldehyde based resinand the one or more fillers and/or extenders to produce a particulate orpowdered binder composition are well known to those skilled in the artand a detailed description of the equipment and process variables areunnecessary. The aldehyde based resin can be mixed, blended, orotherwise combined with the one or more fillers and/or extenders in thepresence of a liquid medium to produce a liquid mixture and the liquidmixture can be spray dried to produce the particulate bindercomposition, where each particulate includes the aldehyde based resinand the one or more fillers and/or extenders.

The aldehyde based resin can be combined with the one or more fillersand/or extenders in the presence of a liquid medium by mechanicalagitation, e.g., magnetic sir bar, impellers, blades, and the like. Inanother example, ultrasonic sound waves can be used to combine the mix,blend, or otherwise combine the aldehyde based resin and the one or morefillers and/or extenders. During mixing of the aldehyde based resin andthe one or more fillers and/or extenders, air or other suitable gas orcombination of gases can be injected into the mixture to furtherincrease the amount of entrained or retained gas therein.

The one or more fillers and/or extenders can also be mixed, blended, orotherwise combined with the aldehyde based binder during the productionof the aldehyde based binder. For example, as discussed and describedbelow, a suitable aqueous phenol-formaldehyde resole resin compositioncan be produced by reacting phenol and formaldehyde in water under analkaline condition so as to yield a phenol-formaldehyde resole resin.The one or more fillers and/or extenders can be combined with one of thereactants, i.e., phenol or formaldehyde, with both of the reactants,i.e., phenol and formaldehyde, or with the aqueous mixture of phenol andformaldehyde.

The processes for producing the particulate binder composition, such asspray-drying, freeze drying, vacuum drying, precipitation, air drying,and dry spinning can also be used to produce particulates that onlyinclude the aldehyde resin. Said another way, particulates of thealdehyde based resin without the presence of the fillers or extenderscan be produced via these known processes and the aldehyde based resinparticulates and particulates of the filler and/or extender can bemixed, blended, or otherwise combined with one another to produce theparticulate binder composition that includes discrete particulates ofthe aldehyde based resin and discrete particulates of the filler and/orthe extender. Accordingly, suitable binder compositions can include, butare not limited to, (1) discrete particulates that include a mixture ofthe aldehyde based resin and at least one of the filler and extender,(2) discrete particulates that include a mixture of the aldehyde basedresin particulates and at least one of the filler and extender inparticulate form, or (3) a combination of (a) particulates that includeboth the aldehyde based resin and at least one of the filler andextender and (b) at least one of aldehyde based resin particulates thatdo not include the filler or extender, particulates of the filler thatdo not include the aldehyde based resin, and particulates of theextender that do not include the aldehyde based resin.

Spray drying refers to the process of atomizing (in the form of smalldroplets) the liquid mixture into a gas stream (often a heated airstream) under controlled temperature conditions and under specificgas/liquid contacting conditions to effect evaporation of the liquidfrom the atomized droplets and production of a dry particulate solidproduct or particulate binder composition or “spray dried bindercomposition.” In the spray drying process, the liquid mixture of thealdehyde based resin and, optionally, the one or more fillers and/orextenders, such as an aqueous mixture of a phenol-formaldehyde resoleresin and one or more fillers and/or extenders, can be atomized to smalldroplets and mixed with hot air (e.g., air at an inlet temperatureusually between about 140° C. and about 250° C.) to evaporate the liquidfrom the droplets. The temperature of the mixture during thespray-drying process is usually close to or greater than the boilingtemperature of the liquid, e.g., the water. An outlet air temperature ofbetween about 60° C. and about 120° C. is common. Due to the curable(thermosetting) character of the aldehyde based resin, adjusting theoperation of the spray-drying process to achieve thorough evaporation ofthe liquid at the lowest possible inlet and outlet temperatures isgenerally desired.

Spray drying is typically carried out with pressure nozzles (nozzleatomization—including two fluid nozzles) or centrifugal or rotaryatomizers operating at high speeds (e.g., a spinning disc). Despite thehigh velocity generation of droplets, a spray dryer is designed so thatthe droplets avoid a much as possible contact with the spray dryer wallunder proper operating procedures. This effect is achieved by a precisebalance of atomizer velocity, air flow, spray dryer dimensions, e.g.,height and diameter, and the design of inlet and outlet means to producea cyclonic flow of gas, e.g., air in the chamber. A pulse atomizer canalso be used to produce the small droplets needed to facilitateevaporation of the liquid. In some cases, it can be desirable to includea flow promoter, such as calcium stearate and/or an aluminosilicatematerial, in the liquid dispersion that is processed in a spray dryersimply to facilitate subsequent handling and transport of the spraydried binder composition (e.g., to avoid clumping).

The aeration level of the liquid mixture, also known as the gas volumefraction (GVF), created by the agitation of the liquid aldehyde basedresin and/or, optionally, the liquid mixture of the aldehyde based resinand the one or more fillers and/or extenders can be selected such thatthe liquid or liquid mixture to be spray-dried has a GVF of at least 1%,at least 2%, at least 3%, at least 4%, at least 5%, at least 6%, atleast 7%, at least 8%, at least 9%, at least 10%, at least 11%, at least12%, at least 13%, at least 14%, at least 15%, at least 16%, at least17%, at least 18%, at least 19%, at least 20%, or more than 20%, basedon the liquid volume of the de-aerated liquid or liquid mixture. Inanother example, the aeration level of the liquid or liquid mixture canrange from a low of about 1 wt %, about 3 wt %, about 5 wt %, or about 7wt % to a high of about 13 w %, about 15 wt %, about 17 wt %, or about19 wt %, with suitable ranges including the combination of any twovalues. Those skilled in the art can select an appropriate technique fordetermining/monitoring the GVF of the liquid or liquid mixture to bespray-dried. For example, suitable techniques are discussed anddescribed in U.S. Pat. Nos. 7,343,818 and 7,596,987. As recognized byone skilled in the art, the level of aeration of a liquid (GVF) also canbe assessed by comparing the difference between the observed aerateddensity and the actual de-aerated density of the liquid.

The particle size and liquid content of the particulate bindercomposition, e.g., prepared via spray drying, is a complex function ofthe air feed rate and temperature, liquid feed rate and temperature,liquid droplet size and the solids concentration of the feed liquid. Theparticulate binder composition can have a liquid content of less thanabout 10 wt %, less than about 8 wt %, less than about 6 wt %, less thanabout 4 wt %, less than about 3 wt %, less than about 2 wt %, or lessthan about 1 wt %. For example, the particulates of the bindercomposition can have a liquid, e.g., water, concentration ranging from alow of about 0.5 wt %, about 1 wt %, about 1.5 wt %, or about 2 wt % toa high of about 5 wt %, about 6 wt %, about 8 wt %, or about 9 wt %,with suitable ranges including the combination of any two values. Inanother example, the liquid, e.g., water, content of the spray-driedpowder can be less than about 6.5 wt %, or less than about 5.5 wt %, orless than about 5 wt %, or less than about 4.5 wt %, or less than about3.5 wt %.

The particle size distribution, liquid, e.g., water, content, and bulkdensity of a spray dried particulate binder composition can becontrolled by operations well known in the spray drying art by variablessuch as feed resin solids content of the liquid mixture, surfacetension, speed of the rotary atomizer, feed rate of the liquid resin,and the temperature differences between the inlet and outlet(atomization gas temperature). Particle size distribution may be animportant factor in production of a particulate binder composition.

The particulate binder composition, e.g., the spray dried binder, can bea free-flowing powder that is easily handled. The particulate bindercomposition can have an average particle size ranging from about 0.1 μmto about 150 μm. For example, the average particle size of theparticulate binder composition can range from a low of about 1 μm, about5 μm, about 10 μm, or about 20 μm to a high of about 50 μm, about 75 μm,about 100 μm, about 125 μm, or about 150 μm, with suitable rangesincluding the combination of any two values. In another example, theparticulate binder composition can have an average particle size rangingfrom a low of about 0.1 μm, about 0.5 μm, about 1 μm, about 2 μm, about3 μm, or about 5 μm to a high of about 20 μm, about 25 μm, about 30 μm,about 35 μm, about 40 μm, about 45 μm, or about 50 μm, with suitableranges including the combination of any two values. In another example,the average particle size of the particulate binder composition canrange from about 3 μm to about 90 μm, about 10 μm to about 80 μm, about20 μm to about 70 μm, about 35 μm to about 75 μm, about 40 μm to about65 μm, about 1 μm to about 20 μm, about 3 μm to about 30 μm, about 10 μmto about 20 μm, about 5 μm to about 40 μm, or about 5 μm to about 35 μm.In another example, about 80 wt % to about 90 wt % of the particulatebinder composition can have a particle size of less than about 100 μm,less than about 85 μm, or less than about 75 μm. In another example,about 60 wt % to about 70 wt % of the particulate binder composition canhave a particle size of less than about 60 μm, less than about 50 μm, orless than about 45 μm. If a desired particle size is not produceddirectly by the technique used to produce the particulate bindercomposition, additional mechanical grinding can be employed to reducethe distribution of the particle sizes further.

Each particulate of the binder composition can include anywhere fromabout 1 to about 100 individual or discrete particles of the fillerand/or extender. For example, the number of discrete particles of thefiller and/or extender distributed throughout each particulate of thebinder composition can range from a low of about 1, about 2, about 3,about 4, or about 5 to a high of about 10, about 20, about 30, about 40,or about 50, with suitable ranges including the combination of any twovalues. In another example, the number of discrete particles of thefiller and/or extender distributed throughout each particulate of thebinder composition can range from 1 to about 2, from 1 to about 3, from1 to about 4, from 1 to about 5, from about 2 to about 10, from about 3to about 6, from about 1 to about 15, or from about 4 to about 12.Alternatively, as discussed and described above or elsewhere herein,each particulate of the binder composition can be either the aldehydebased resin, the filler, or the extender. Said another way, theparticulate binder composition can be or include a mixture of discreteparticulates composed of the aldehyde based resin, i.e., the filler andextender are not included in the discrete particles composed of thealdehyde based resin, and discrete particulates composed of the filler,the extender, or a combination of the filler and the extender.

The individual particulates of the binder composition can have the samecomposition throughout. In other words, any given particulate of thebinder composition can have the same composition throughout thatparticulate. Said another way, the composition of the particulates caninclude both the filler and/or extender and the aldehyde based resindispersed throughout the body of the particulate. Alternatively, theindividual particulates of the binder composition can have differentcompositions with respect to one another. For example, some of theindividual particulates (first plurality of particulates) can becomposed of the aldehyde based resin without the presence of the filleror extender therein and some of the individual particulates (secondplurality of particulates) can be composed of the filler and/or extenderwithout the presence of the aldehyde based resin therein.

When the individual particulates of the particulate binder compositioninclude both the aldehyde based resin and at least one of the filler orthe extender, the amount of the one or more fillers and/or extenders ineach particulate of the binder composition can be the same or differentwith respect to any two individual particles or particulates. The amountof the one or more fillers and/or extenders in the particulates of thebinder composition can range from about 0.5 wt % to about 30 wt %, basedon the combined weight of the aldehyde based resin solids and thefillers and/or extenders. For example, the amount of the one or morefillers and/or extenders in the particulates of the binder compositioncan range from a low of about a low of about 1 wt %, about 3 wt %, about5 wt %, about 7 wt %, or about 9 wt % to a high of about 14 wt %, about16 wt %, about 18 wt %, about 20 wt %, about 22 wt %, about 24 wt %, orabout 26 wt %, based on the combined weight of the aldehyde based resinsolids and the fillers and/or extenders, with suitable ranges includingthe combination of any two values. In another example, the amount of theone or more fillers and/or extenders in the particulates of the bindercomposition can range from about 2 wt % to about 7 wt %, about 4 wt % toabout 12 wt %, about 8 wt % to about 17 wt %, about 10 wt % to about 22wt %, or about 4 wt % to about 16 wt %, based on the combined weight ofthe aldehyde based resin solids and the fillers and/or extenders. Inanother example, the particulates of the binder composition can includefrom about 1 wt % to about 26 wt %, or about 2 wt % to about 20 wt %, orabout 4 wt % to about 16 wt % of the one or more fillers, from about 1wt % to about 26 wt %, or about 2 wt % to about 20 wt %, or about 4 wt %to about 16 wt % of the one or more extenders, and/or from about 1 wt %to about 26 wt %, or about 2 wt % to about 20 wt %, or about 4 wt % toabout 16 wt % of a combination of the one or more fillers and one ormore extenders, based on the combined weight of the aldehyde based resinsolids and the fillers and/or extenders.

When the particulate binder composition includes a mixture of discretealdehyde based resin particulates, i.e., the discrete aldehyde basedresin particulates do not include the filler or the extender, (firstplurality of particulates), and discrete filler and/or extenderparticulates (second plurality of particulates), the amount of the oneor more fillers and/or extenders in the particulate binder compositioncan range from about 0.5 wt % to about 30 wt %, based on the combinedweight of the discrete aldehyde based resin particulates and thediscrete filler and/or extender particulates. For example, the amount ofthe one or more fillers and/or extenders in the particulate bindercomposition that includes a mixture of discrete aldehyde based resinparticulates and discrete filler and/or extender particulates can rangefrom a low of about a low of about 1 wt %, about 3 wt %, about 5 wt %,about 7 wt %, or about 9 wt % to a high of about 14 wt %, about 16 wt %,about 18 wt %, about 20 wt %, about 22 wt %, about 24 wt %, or about 26wt %, based on the combined weight of the discrete aldehyde based resinparticulates and the discrete filler and/or extender particulates, withsuitable ranges including the combination of any two values. In anotherexample, the amount of the one or more fillers and/or extenders in theparticulate binder composition that includes a mixture of discretealdehyde based resin particulates and discrete filler and/or extenderparticulates can range from about 2 wt % to about 7 wt %, about 4 wt %to about 12 wt %, about 8 wt % to about 17 wt %, about 10 wt % to about22 wt %, or about 4 wt % to about 16 wt %, based on the combined weightof the discrete aldehyde based resin particulates and the discretefiller and/or extender particulates. In another example, the bindercomposition composed of a mixture of discrete aldehyde based resinparticulates and discrete filler and/or extender particulates caninclude from about 1 wt % to about 26 wt %, or about 2 wt % to about 20wt %, or about 4 wt % to about 16 wt % of the one or more fillers, fromabout 1 wt % to about 26 wt %, or about 2 wt % to about 20 wt %, orabout 4 wt % to about 16 wt % of the one or more extenders, and/or fromabout 1 wt % to about 26 wt %, or about 2 wt % to about 20 wt %, orabout 4 wt % to about 16 wt % of a combination of the one or morefillers and one or more extenders, based on the combined weight of thediscrete aldehyde based resin particulates and the discrete fillerand/or extender particulates.

In at least one example, the particulate binder composition can includea mixture of a first particulate binder composition containing a firstaldehyde based resin and one or more fillers and a second particulatebinder composition containing a second aldehyde based resin and one ormore extenders. The first aldehyde based resin and the second aldehydebased resin can be the same or different. For example, both the firstand second aldehyde based resins can be a phenol-formaldehyde resoleresin. In another example, either the first aldehyde based resin or thesecond aldehyde based resin can be a phenol-formaldehyde resole resinand the other can be a urea-formaldehyde resin. In at least one otherexample, the particulate binder composition can include a mixture of afirst particulate binder composition containing a first aldehyde basedresin and a first filler and a second particulate binder compositioncontaining a second aldehyde based resin and a second filler and/or oneor more extenders. The first aldehyde based resin and the secondaldehyde based resin can be the same or different. The first filler andthe second filler can be the same or different. In at least one otherexample, the particulate binder composition can include a mixture of afirst particulate binder composition containing a first aldehyde basedresin and a first extender and a second binder composition containing asecond aldehyde based resin and a second extender and/or one or morefillers. The first aldehyde based resin and the second aldehyde basedresin can be the same or different. The first extender and the secondextender can be the same or different.

Similarly, the binder composition that includes a mixture of discretealdehyde based resin particulates and discrete filler and/or extenderparticulates can include one or more aldehyde based resin particulatesand at least one of the one or more discrete filler particulates, andthe one or more discrete extender particulates. For example, theparticulate binder composition can include a mixture of one or morefirst discrete aldehyde based resin particulates, one or more seconddiscrete aldehyde based resin particulates, and at least one of thediscrete filler particulates and the discrete extender particulates.

The particulate binder composition can have a packed bulk densityranging from about 0.15 g/cm³ to about 0.85 g/cm³. For example, thepacked bulk density of the particulate binder composition can range froma low of about 0.15 g/cm³, about 0.3 g/cm³, about 0.35 g/cm³, about 0.4g/cm³, or about 0.45 g/cm³ to a high of about 0.6 g/cm³, about 0.65g/cm³, about 0.7 g/cm³, about 0.75 g/cm³, about 0.8 g/cm³, or about 0.85g/cm³, with suitable ranges including the combination of any two values.In another example, the particulate binder composition can have a packedbulk density of about 0.45 g/cm³ to about 0.57 g/cm³, about 0.4 g/cm³ toabout 0.6 g/cm³, about 0.55 g/cm³ to about 0.75 g/cm³, or about 0.35g/cm³ to about 0.65 g/cm³. In another example, the particulate bindercomposition can have a packed bulk density of less than about 0.68g/cm³, less than about 0.6 g/cm³, less than about 0.58 g/cm³, or lessthan about 0.57 g/cm³.

The particulate binder composition can have a stroke time ranging form alow of about 1 second, about 3 seconds, or about 5 seconds to a high ofabout 25 seconds, about 30 seconds, or about 35 seconds, with suitableranges including the combination of any two values. For example, theparticulate binder composition can have a stroke time ranging from about5 seconds to about 25 seconds, about 8 seconds to about 16 seconds, orabout 10 seconds to about 18 seconds.

The particulate binder composition can have a fusion diameter rangingfrom a low of about 14 mm, about 18 mm, about 21 mm, or about 25 mm to ahigh about 45 mm, about 50 mm, about 55 mm, or about 60 mm. For example,the particulate binder composition can have a fusion diameter of about15 mm to about 40 mm, about 20 mm to about 35 mm, about 25 mm to about30 mm, about 25 mm to about 50 mm, or about 15 mm to about 35 mm.

One or more additional additives or modifiers can be combined with theparticulate binder composition and/or the liquid mixture of the aldehydebased resin and the filler and/or extender and/or any one or more of theliquid aldehyde based resin, the filler, and the extender when thebinder composition includes a mixture of discrete aldehyde based resinparticulates and discrete filler and/or extender particulates.Illustrative additives or modifiers can include, but are not limited to,catalysts, other cure promoters or accelerants (e.g., alkali metal andalkaline earth metal carbonates and hydroxides, such as sodiumhydroxide), thickeners, adduct-forming agents (e.g., urea), tackpromoters (e.g., borax), foaming agents, defoamers, and/or surfactants.For example, one or more surfactants, such as nonionic surfactants, canbe combined with the liquid mixture of the aldehyde based resin and theone or more fillers and/or extenders to adjust or control a packed bulkdensity of the spray dried binder composition, as discussed anddescribed in U.S. Patent Application Publication No. 2011/0136947.

The aldehyde based resin can include, but is not limited to, one or moreurea-aldehyde resins, one or more melamine-aldehyde resins, one or morephenol-aldehyde resins, e.g., phenol-formaldehyde novolac resin and/orphenol-formaldehyde resole resin, one or more dihydroxybenzene or“resorcinol”-aldehyde resins, one or more phenol-resorcinol-aldehyderesins, one or more melamine-urea-aldehyde resins, one or morephenol-urea-aldehyde resins, or any combination thereof. In one example,the aldehyde based resin can be or include a phenol-formaldehyde resin.The phenol-formaldehyde resin can be a phenol-formaldehyde resole resin.

Referring to phenol-formaldehyde resole resin in particular, the resincan be a phenol-formaldehyde resin prepared under liquid, e.g., aqueous,alkaline reaction conditions using a molar excess of formaldehyde. Forexample, the phenol-formaldehyde resole resin can have a molar ratio offormaldehyde to phenol ranging from a low of about 1.7, about 1.8, orabout 1.9 to a high of about 2.5, about 2.6, or about 2.7, with suitableranges including the combination of any two values. For example,suitable phenol-aldehyde resins can have a molar ratio of formaldehydeto phenol ranging from about 1.8 to about 2.65, about 2.1 to about 2.65,about 2.2 to about 2.5, about 2.3 to about 2.5, about 2.4 to about 2.55,about 2.45 to about 2.5, about 2.4 to about 2.5, or about 2.05 to about2.55. Phenol-formaldehyde resins prepared within such a molar ratiorange typically have a weight average molecular weight in the range ofabout 1,000 Daltons to about 8,000 Daltons. Such resin compositions arecommonly referred to as “resole resins.” As used herein, the term“formaldehyde to phenol molar ratio” and “F:P molar ratio” are usedinterchangeably and refer to the total amount, in moles, of theformaldehyde compound(s) combined with each mole of the phenolcompound(s) and assumes no loss of the formaldehyde or phenol compoundsthrough volatilization, hydrolysis, or other means.

The phenol-formaldehyde resole resin can have can have a pH ranging froma low of about 7, about 8, or about 9 to a high of about 11, about 12,or about 13, with suitable ranges including the combination of any twovalues. The phenol-formaldehyde resole resin can have a viscosityranging from a low of about 50 cP, about 75 cP, about 100, cP, about 150cP, about 200 cP, or about 250 cP to a high of about 400 cP, about 500cP, about 600 cP, about 700 cP, about 1,000 cP, about 1,250 cP, or about1,500 cP, with suitable ranges including the combination of any twovalues. The viscosity of any one or more of the aldehyde based resinsdiscussed and described herein can be determined using a BrookfieldViscometer at a temperature of about 25° C. For example, a BrookfieldViscometer, Model DV-II+, with a small sample adapter can be used. Thesmall sample adapter can allow the sample to be cooled or heated by thechamber jacket to maintain the temperature of the sample surrounding thespindle at a temperature of about 25° C.

A suitable aqueous phenol-formaldehyde resole resin composition can beproduced by reacting phenol and formaldehyde in water under an alkalinecondition so as to yield a phenol-formaldehyde resole resin having aweight average molecular weight of about 1,000 to about 8,000 Daltons.For example, the weight average molecular weight of thephenol-formaldehyde resole resin can range from a low of about 1,000Daltons, about 2,500 Daltons, or about 3,000 Daltons to a high of about5,000 Daltons, about 6,000 Daltons, about 7,000 Daltons, with suitableranges including the combination of any two values. In another example,the weight average molecular weight of the phenol-formaldehyde resoleresin can be between about 1,500 Daltons and about 5,000 Daltons, about1,800 Daltons to 4,500 Daltons, or about 2,000 Daltons to about 4,000Daltons.

The weight average molecular weight of the phenol-formaldehyde resoleresin can be determined by gel permeation chromatography (GPC). The GPCmethod can use tetrahydofuran as a solvent/diluent and a system of twomixed C chromatographic columns preceding a 500 Angstroms PLgel column,all available from Polymer Laboratories (now part of Varian, Inc.). Thecolumn arrangement is calibrated using a range of polystyrene standards.For determining the weight average molecular weight of a particularresin sample, the sample is injected along with polystyrene, such ashaving a molecular weight of about 250,000 Daltons, and toluene as aninternal standard. A Model 759A Absorbance Detector from AppliedBiosystems is used to monitor the column output and assist the molecularweight determination. The method of determining the molecular weight ofa phenol-formaldehyde resin is well understood by those skilled in theart.

Any known method capable of producing a liquid phenol-formaldehyderesole resin can be used. Suitable methods for synthesizing a liquidphenol-formaldehyde resole resin composition can include both singlestep processes and multi-step or “programmed” processes (i.e., stagedmonomer/catalyst addition). While batch operations are the standard,continuous processes are also possible. Standard conditions, proceduresand reactants for making an aqueous resole resin, well-known to thoseskilled in the art, can be used.

The phenol-formaldehyde resole resin can be produced by adding to areactor containing phenol, an amount of formaldehyde sufficient toestablish an initial formaldehyde to phenol molar ratio (F:P) in therange of about 0.6:1 to about 1.6:1. The formaldehyde can then bereacted, under an alkaline reaction condition, with the phenol toproduce the phenol-formaldehyde resole resin. Following the initialreaction, an additional amount of formaldehyde can be added to thereaction mixture, sufficient to establish a cumulative formaldehyde tophenol (F:P) in the range of about 2:1 to about 2.65:1.

The reaction can be carried out in a liquid medium. Illustrative liquidmediums can include, but are not limited to, water, alcohols, glycols,acetonitrile, or any combination thereof. Suitable alcohols can include,but are not limited to, methanol, ethanol, propanol, butanol, or anycombination thereof. Suitable glycols can include, but are not limitedto, ethylene glycol, propylene glycol, or a combination thereof. As usedherein, the terms “aqueous medium” and “aqueous liquid” can be orinclude water and/or mixtures composed of water and/or otherwater-miscible solvents. Illustrative water-miscible solvents caninclude, but are not limited to, alcohols, ethers, amines, other polaraprotic solvents, and the like.

The aqueous phenol-formaldehyde resole resin composition, as produced,can have a solids content of about 25 wt % to about 65 wt % solids,about 30 wt % to about 65 wt %, about 25 wt % to about 50 wt %, about 30wt % to about 50 wt % solids, about 25 wt % to about 45 wt %, about 30wt % to about 45 wt %, or about 35 wt % to about 45 wt % solids. As usedherein, the solids content of the phenol-formaldehyde resole resin whencombined with a liquid medium, as understood by those skilled in theart, can be measured by determining the weight loss upon heating a smallsample, e.g., 1-5 grams, of the liquid phenol-formaldehyde resole resinto a suitable temperature, e.g., 105° C., and for a length of timesufficient to remove the liquid. By measuring the weight of the samplebefore and after heating, the percent solids in the sample can bedirectly calculated or otherwise estimated.

Conveniently, a batch process can be used to synthesize a suitableliquid phenol-formaldehyde resole resin composition by a single-stagealkaline condensation of phenol and formaldehyde under vacuum reflux ata temperature between about 50° C. to about 100° C., preferably aboveabout 70° C., and more preferably above about 80° C.

The phenol-formaldehyde resole resin can be modified by the postaddition of caustic and/or other additives such as urea and/or ammonia,which often are added to reduce the residual level of free, unreactedformaldehyde in the synthesized resin. Other additives can include, butare not limited to, dispersants, biocides, viscosity modifiers, pHadjusters, coupling agents, lubricants, defoamers, surfactants, and thelike.

When preparing a liquid phenol-formaldehyde resole resin composition, analkaline catalyst can be used to promote the reaction of formaldehydewith phenol. Illustrative alkaline catalysts can include, but are notlimited to, alkali metal hydroxides, alkali metal carbonates, alkalineearth oxides, or any combination thereof. Illustrative alkali metalhydroxides can include, but are not limited to, sodium hydroxide,lithium hydroxide, potassium hydroxide, or any combination thereof.Generally sodium hydroxide is used based on its cost, availability, andsuitability. Illustrative alkali metal carbonates can include, but arenot limited to, sodium carbonate, lithium carbonate, potassiumcarbonate, or a combination thereof. Illustrative alkaline earth metalhydroxides can include, but are not limited to, magnesium hydroxide,calcium hydroxide, barium hydroxide, organic amines, or any combinationthereof. Illustrative alkaline earth oxides can include, but are notlimited to, calcium oxide, strontium oxide, barium oxide, or anycombination thereof. In one or more embodiments, the catalyst can beused in a low amount, but in an effective amount to catalyze thereaction.

The liquid phenol-formaldehyde resole resin can also be prepared usingstaged addition processes, which are well known to those skilled in theart. When preparing the liquid phenol-formaldehyde resole resin in thisway, formaldehyde can be added gradually to the phenol, and/or phenolcan be added gradually to the formaldehyde and/or the alkaline catalystcan be added gradually to a mixture of formaldehyde and phenol topromote a controlled polymerization.

In any of these synthesis processes, the phenol-formaldehyde resoleresin can be prepared using reactants that are commercially available inmany forms such as solid, liquid, and/or gas. Formaldehyde is availableas paraformaldehyde (a solid, polymerized formaldehyde) and moreconveniently as formalin solutions (aqueous solutions of formaldehyde,sometimes with methanol, usually in 37%, 44%, or 50% formaldehydeconcentrations). Formaldehyde gas can also be used alone or incombination with sold and/or liquid forms of formaldehyde. In at leastone specific embodiment, the formaldehyde can be partially or completelyreplaced with one or more other aldehyde compounds. Other aldehydecompounds can include, but are not limited to, acetaldehyde,propionaldehyde, butyraldehyde, furfuraldehyde, benzaldehyde, or anycombination thereof. One or more other aldehyde compounds, such asglyoxal can also be used in place of or in combination with formaldehydeand/or other aldehyde compounds. In at least one embodiment, a formalinsolution low in methanol can be used as the formaldehyde source.

Phenol used for making the phenol-formaldehyde resole resins can bereplaced, partially or completely, with other phenolic compoundsun-substituted at either the two ortho positions or at one ortho and thepara position. These unsubstituted positions can facilitate the desiredpolymerization reaction(s). Any one, all, or none of the remainingcarbon atoms of the phenol ring can be substituted in a conventionalfashion. The nature of the substituents can vary widely, and it is onlynecessary that the substituent not interfere in the polymerization ofthe aldehyde with the phenol at the ortho and/or para positions.Substituted phenols which optionally can be employed in the formation ofthe liquid phenol-formaldehyde resole resin can include, but are notlimited to, alkyl substituted phenols, aryl substituted phenols,cycloalkyl substituted phenols, alkenyl substituted phenols, alkoxysubstituted phenols, aryloxy substituted phenols, and halogensubstituted phenols, the foregoing substituents possibly containing from1 to about 26, from 1 to about 20, from 1 to about 15, or from 1 toabout 9 carbon atoms.

Specific examples of suitable phenolic compounds for replacing a portionor all of the phenol used in preparing the phenol-formaldehyde resincompositions can include, but are not limited to, bis-phenol A,bis-phenol F, o-cresol, m-cresol, p-cresol, 3,5-5 xylenol, 3,4-xylenol,3,4,5-trimethylphenol, 3-ethyl phenol, 3,5-diethyl phenol, p-butylphenol, 3,5-dibutyl phenol, p-amyl phenol, p-cyclohexyl phenol, p-octylphenol, 3,5 dicyclohexyl phenol, p-phenyl phenol, p-phenol,3,5-dimethoxy phenol, 3,4,5 trimethoxy phenol, p-ethoxy phenol, p-butoxyphenol, 3-methyl-4-methoxy phenol, p-phenoxy phenol, naphthol, anthranoland substituted derivatives thereof.

The phenol-formaldehyde resole resin composition can have an alkalinity,i.e., contains a base, in the range of about 0.5% to about 15%, about 1%to about 12%, or about 2% to 8%, e.g., about 6%, based on the weight ofthe liquid resole resin composition, when the base is sodium hydroxide.If a different base is used, the alkalinity content can be proportionedto be equivalent on a molar weight basis to the above noted range basedon sodium hydroxide. For example, to attain the equivalent of analkalinity of 6% sodium hydroxide, i.e., 6 grams of sodium hydroxide in100 grams of liquid resin, about 8.4 grams of potassium hydroxide in 100grams of the resin solution would be required. As noted above, the baseconveniently may be an alkali metal or alkaline earth metal compoundsuch as a hydroxide, a carbonate, or an oxide.

Similar to phenol-formaldehyde resole resin, suitable urea-formaldehyderesins, melamine-formaldehyde, phenol-formaldehyde novolac resins, andresorcinol-formaldehyde resins can be prepared from melamine, phenol,and resorcinol monomers, respectively, and formaldehyde monomers or frommelamine-formaldehyde, phenol-formaldehyde, and resorcinol-formaldehydeprecondensates. Urea, melamine, and resorcinol reactants arecommercially available in many forms and any form that can react withthe other reactants and does not introduce extraneous moietiesdeleterious to the desired reaction and reaction product can be used inthe preparation of the second copolymer.

Suitable forms of urea, if present in the aldehyde based resin, solidurea, such as prill and urea solutions, typically aqueous solutions, arecan be used. Further, urea may be combined with another moiety, mosttypically formaldehyde and urea-formaldehyde adducts, often in aqueoussolution. Any form of urea or urea in combination with formaldehyde canbe used to make a urea-formaldehyde resin. Both urea prill and combinedurea-formaldehyde products are preferred, such as UFC. These types ofproducts can be as discussed and described in U.S. Pat. Nos. 5,362,842and 5,389,716, for example.

Many suitable aldehyde based resins are commercially available. Forexample, suitable aldehyde based resins can include, but are not limitedto, resins sold by Georgia-Pacific Chemicals LLC (e.g., LEAF™,RESI-STRAN®, REST-BOND®, WOODWELD®, RESORSABOND®, and REST-MIX®. Thesealdehyde based resins can be prepared in accordance with well knownmethods and contain reactive methylol groups which upon curing formmethylene or ether linkages. Such methylol-containing adducts mayinclude N,N′-dimethylol, dihydroxymethylolethylene;N,N′bis(methoxymethyl), N,N′-dimethylolpropylene;5,5-dimethyl-N,N′dimethylolethylene; N,N′-dimethylolethylene; and thelike.

Urea-formaldehyde resins can include from about 45% to about 70%, andpreferably, from about 55% to about 65% non-volatiles, generally have aviscosity of about 50 centipoise (“cP”) to about 1,200 cP, normallyexhibit a pH of about 7 to about 9, preferably about 7.5 to about 8.5,and often have a free formaldehyde level of not more than about 3.0%,and a water dilutability of about 1:1 to about 100:1, preferably about5:1 and above.

Melamine, if present in the aldehyde based resin, can also be providedin many forms. For example, solid melamine, such as prill and/ormelamine solutions can be used. Although melamine is specificallyreferred to, the melamine can be totally or partially replaced withother aminotriazine compounds. Other suitable aminotriazine compoundscan include, but are not limited to, substituted melamines,cycloaliphatic guanamines, or combinations thereof. Substitutedmelamines include the alkyl melamines and aryl melamines that can bemono-, di-, or tri-substituted. In the alkyl substituted melamines, eachalkyl group can contain 1-6 carbon atoms and, preferably 1-4 carbonatoms. Illustrative examples of the alkyl-substituted melamines caninclude, but are not limited to, monomethyl melamine, dimethyl melamine,trimethyl melamine, monoethyl melamine, and 1-methyl-3-propyl-5-butylmelamine. In the aryl-substituted melamines, each aryl group can contain1-2 phenyl radicals and, preferably, one phenyl radical. Illustrativeexamples of aryl-substituted melamines can include, but are not limitedto, monophenyl melamine and diphenyl melamine. Any of the cycloaliphaticguanamines can also be used. Suitable cycloaliphatic guanamines caninclude those having 15 or less carbon atoms. Illustrativecycloaliphatic guanamines can include, but are not limited to,tetrahydrobenzoguanamine, hexahydrobenzoguanamine,3-methyl-tetrahydrobenzoguanamine, 3-methylhexahydrobenzoguanamine,3,4-dimethyl-1,2,5,6-tetrahydrobenzoguanamine, and3,4-dimethylhexahydrobenzoguanamine and mixtures thereof. Mixtures ofaminotriazine compounds can include, for example, melamine and analkyl-substituted melamine, such as dimethyl melamine, or melamine and acycloaliphatic guanamine, such as tetrahydrobenzoguanamine.

The resorcinol component, if present in the aldehyde based resin, can beprovided in a variety of forms. For example, the resorcinol componentcan be provided as a white/off-white solid or flake and/or theresorcinol component can be heated and supplied as a liquid. Any form ofthe resorcinol can be used with any form of the aldehyde component tomake the resorcinol-aldehyde copolymer. The resorcinol component can beresorcinol itself (i.e., Benzene-1,3-diol). Suitable resorcinolcompounds can also be described as substituted phenols. The solidscomponent of a liquid resorcinol-formaldehyde copolymer can range fromabout 45 wt % to about 75 wt %. Liquid resorcinol-formaldehydecopolymers can have a viscosity that varies widely, e.g., from about 200cP to about 20,000 cP. Liquid resorcinol copolymers typically have adark amber color.

As used herein, the term “filler” refers to materials that can be addedto the aldehyde based resin and/or materials that can be mixed withdiscrete aldehyde based resin particulates that occupy volume but do notcontribute or do not substantially contribute to bonding properties ofthe binder composition. Suitable fillers can be or include, but are notlimited to, ground, crushed, pulverized, other otherwise reduced intoparticulate form nut shells, seed shells, fruit pits, animal bones,milwhite, clay, or any combination thereof. Other suitable fillers caninclude, but are not limited to, inorganic oxides, e.g., silica and/oralumina, glass spheres or particulates, and the like.

Illustrative nut shells can include, but are not limited to, walnutshells, pecan shells, almond shells, ivory nut shells, brazil nutshells, ground nut (peanut) shells, pine nut shells, cashew nut shells,sunflower seed shells, Filbert nut (hazel nut) shells, macadamia nutshells, soy nut shells, pistachio nut shells, pumpkin seed shells, orthe like, or any combination thereof. Illustrative seed shells(including fruit pits), can include, but are not limited to, the seedshells of fruit, e.g., plum, peach, cherry, apricot, olive, mango,jackfruit, guava, custard apples, pomegranates, and watermelon, groundor crushed seed shells of other plants such as maize (e.g., corn cobs orcorn kernels), wheat, rice, jowar, or the like, or any combinationthereof. More particular examples of suitable fillers can include, butare not limited to, wheat shell, corn husk, peanut shell, or anycombination thereof. For example, the nut shells and/or seed shells canbe ground or powdered, e.g., flour form. In one example, suitable floursderived from nut shells can include, but are not limited to, walnutshell flour, pecan shell flour, almond shell flour, or any combinationthereof. Illustrative flour derived from the seed shells of fruits caninclude, but are not limited to, apricot pit shell flour, peach pitshell flour, prune pit shell flour, or any combination thereof.

As used herein, the term “extender” refers to materials that can beadded to the aldehyde based resin and/or materials that can be mixedwith discrete aldehyde based resin particulates that occupy volume andalso contribute to bonding properties of the binder composition. Oneexample of a suitable extender can be a material that includes one ormore proteins. The protein can contribute to the crosslinking of thebinder composition during at least partial cure thereof. Suitableextenders can include, but are not limited to, corn flour, soy flour,wheat flour, spray dried blood, or any combination thereof.

The soy flour can be a raw soy protein and/or a soy protein modified asdiscussed and described in U.S. Pat. No. 6,497,760. Raw soy protein canbe in the form of ground whole beans (including the hulls, oil, protein,minerals, etc.), a meal (extracted or partially extracted), a flour(i.e., generally containing less than about 1.5% oil and about 30-35%carbohydrate), or an isolate (i.e., a substantially pure protein flourcontaining less than about 0.5% oil and less than about 5%carbohydrate). Suitable soy protein can be derived from any source ofsoy protein such as soybean concentrate or soybean meal. Protein-richsoybean-derived flours, such as soy protein isolate, protein concentrateand ordinary defatted soy flour, which contain in the range of about20-95% protein, can be used. Of these, ordinary soy flour is the mostabundant and cost-effective. The source of soy protein (soy flour) canbe essentially free of functional urease. Information on soy protein canbe found in, for example, Kirk-Othmer, Encyclopedia of ChemicalTechnology, Fourth Edition, Volume 22, pp. 591-619 (1997). Modified soyprotein can be modified with either of two classes of modifiers. Thefirst class of modifiers can include saturated and unsaturated alkalimetal C₈-C₂₂ sulfate and sulfonate salts. Two preferred modifiers inthis class are sodium dodecyl sulfate and sodium dodecylbenzenesulfonate. The second class of modifiers includes compounds having theformula R₂NC(═X)NR₂, where each R is individually selected from thegroup consisting of H and C₁-C₄ saturated and unsaturated groups, and Xis selected from the group consisting of O, NH, and S. The C₁-C₄saturated groups refer to alkyl groups (both straight and branchedchain) and the unsaturated groups refer to alkenyl and alkynyl groups(both straight and branched chain). Illustrative modifiers in the secondgroup can include, but are not limited to, urea and guanidinehydrochloride. Other suitable extenders and preparation thereof caninclude, but are not limited to, those discussed and described in U.S.Pat. Nos. 2,507,465; 2,492,510; 2,781,286; 3,285,805; 3,957,703;4,070,314; 4,244,846; and 4,778,530.

The fillers and/or extenders can have an average particle size rangingfrom about 0.1 μm to about 100 μm. For example, the average particlesize of the fillers and/or extenders can range from a low of about 1 μm,about 3, about 5 μm, about 8 μm, or about 10 μm to a high of about 30μm, about 40 μm, about 50 μm, or about 60 μm, with suitable rangesincluding the combination of any two values. In another example, theaverage particle size of the fillers and/or extenders can range fromabout 7 μm to about 30 μm, about 10 to about 30, about 20 μm to about 35μm, about 0.1 μm to about 10 μm, about 5 μm to about 45 μm, about 15 toabout 35, or about 10 μm to about 50 μm.

If the binder composition includes one or more fillers and one or moreextenders, the amount of the filler(s) and extender(s), relative to oneanother, can widely vary. For example, if the binder compositionincludes both the filler and extender, the amount of the filler in thebinder composition can range from about 0.1 wt % to about 99.9 wt %,based on the combined weight of the filler(s) and the extender(s). Inanother example, in a binder composition containing both a filler and anextender, the binder composition can have a concentration of the fillerranging from a low of about 0.5 wt %, about 1 wt %, about 5 wt %, about10 wt %, or about 20 wt % to a high of about 30 wt %, about 40 wt %,about 50 wt %, about 60 wt %, about 70 wt %, about 80 wt %, about 90 wt%, or about 95 wt %, based on the combined weight of the filler(s) andextender(s), with suitable ranges including the combination of any twovalues.

The particulate binder composition, e.g., the spray dried bindercomposition and/or a mixture of the discrete aldehyde resin particulatesand at least one of discreet filler and extender particulates, can beused in the preparation of a variety of lignocellulose compositeproducts. Methods for using the particulate binder compositions formaking wood composites are well-known to those skilled in the art. Heatand pressure can be applied to a mat of wood pieces, e.g., wood wafersand/or oriented strands of wood, at least partially coated with thepowdered resin in order to cure the resin and form a composite product.Conventional temperatures, time periods, pressures, and quantity ofparticulate binder composition can be used.

For example, the particulate binder composition can be applied to aplurality of lignocellulose substrates to form a bindercomposition/substrate mixture or “furnish.” The lignocellulosesubstrates can be formed into a desired shape before and/or afterapplication of the particulate binder composition, and the particulatebinder composition can be at least partially cured to produce acomposite product. At least partially curing the particulate bindercomposition can include applying heat and/or pressure thereto. Inanother example, the particulate binder composition can be applied to aplurality of lignocellulose or wood particles and at least partiallycured to produce cellulose based or wood based products or composites.In another example, the particulate binder composition can be applied towood or other lignocellulose based veneers and/or substrates and thebinder composition can be at least partially cured to adhere theveneer(s) and/or substrate(s) to one another. In another example, theparticulate binder composition can be applied to a plurality of randomlyoriented or non-oriented lignocellulose substrates, e.g., fibers, chips,flakes, strands, or the like, or any combination thereof, formed into amat or board shape, and then at least partially cured to produce alignocellulose mat or board. In another example, the particulate bindercomposition can be applied to a plurality of oriented lignocellulosefibers, chips, flakes, strands, or the like, or any combination thereof,formed into a mat or board shape, and then at least partially cured toproduce a lignocellulose mat or board. For example, the mat or boardshape can include two or more layers of the lignocellulose substrateswith each layer have substantially aligned substrates and with thelignocellulose substrates in each alternating of adjacent layer orientedperpendicularly to the one another.

The amount of the particulate binder composition applied to thelignocellulose substrates can range from a low of about 1 wt %, about 2wt %, about 3 wt %, about 4 wt %, about 5 wt % or about 6 wt % to a highof about 10 wt %, about 12 wt %, about 15 wt %, or about 20 wt %, basedon dry a weight of the lignocellulose substrates, with suitable rangesincluding the combination of any two values. For example, a compositeproduct of the lignocellulose substrates can contain from about 5 wt %to about 15 wt %, about 8 wt % to about 14 wt %, about 10 wt % to about12 wt %, or about 7 wt % to about 10 wt % binder composition, based on adry weight of the lignocellulose substrates. In another example, acomposite product of the lignocellulose substrates can contain fromabout 1 wt % to about 4 wt %, about 1.5 wt % to about 5 wt %, about 2 wt% to about 4 wt %, about 2 wt % to about 6 wt %, or about 0.5 wt % toabout 5.5 wt % binder composition, based on a dry weight of thelignocellulose substrates.

As used herein, the terms “curing,” “cured,” and similar terms areintended to embrace the structural and/or morphological change thatoccurs in a the binder composition, such as by covalent chemicalreaction (crosslinking), ionic interaction or clustering, improvedadhesion to the substrate, phase transformation or inversion, and/orhydrogen bonding when the binder composition is at least partially curedto cause the properties of a flexible, porous substrate, such as a mator blanket of fibers, especially glass fibers, and/or a rigid orsemi-rigid substrate, such as a wood or other cellulose containing boardor sheet, to which an effective amount of the binder composition hasbeen applied, to be altered.

The lignocellulose substrate (material that includes both cellulose andlignin) can include, but is not limited to, straw, hemp, sisal, cottonstalk, wheat, bamboo, sabai grass, rice straw, banana leaves, papermulberry (i.e., bast fiber), abaca leaves, pineapple leaves, espartograss leaves, fibers from the genus Hesperaloe in the family Agavaceaejute, salt water reeds, palm fronds, flax, ground nut shells, hardwoods,softwoods, recycled fiberboards such as high density fiberboard, mediumdensity fiberboard, low density fiberboard, oriented strand board,particleboard, animal fibers (e.g., wool, hair), recycled paper products(e.g., newspapers, cardboard, cereal boxes, and magazines), or anycombination thereof. Suitable woods can include softwoods and/orhardwoods. Illustrative types of wood can include, but are not limitedto, alder, ash, aspen, basswood, beech, birch, cedar, cherry,cottonwood, cypress, elm, fir, gum, hackberry, hickory, maple, oak,pecan, pine, poplar, redwood, sassafras, spruce, sycamore, walnut, andwillow. The lignocellulose substrates can have a moisture concentrationranging from about 1 wt % to about 25 wt %. For example, thelignocellulose substrates can have a moisture concentration ranging froma low of about 2 wt %, about 3 wt %, about 4 wt %, or about 5 wt % to ahigh of about 10 wt %, about 13 wt %, about 16 wt %, or about 19 wt %,or about 22 wt %, with suitable ranges including the combination of anytwo values.

The starting material, from which the lignocellulose substrates can bederived from, can be reduced to the appropriate size or dimensions byvarious processes such as hogging, grinding, hammer milling, tearing,shredding, and/or flaking. Suitable forms of the lignocellulosesubstrates can include, but are not limited to, chips, fibers, shavings,sawdust or dust, or the like. The lignocellulose substrates can have alength ranging from a low of about 0.05 mm, about 0.1 mm, about 0.2 mmto a high of about 1 mm, about 5 mm, about 10 mm, about 20 mm, about 30mm, about 40 mm, about 50 mm, or about 100 mm, with suitable rangesincluding the combination of any two values. The starting material, fromwhich the lignocellulose substrates can be derived from, can also beformed into the appropriate size or dimensions by skiving, cutting,slicing, sawing, or otherwise removing a thin layer or sheet from asource of lignocellulose material, e.g., a wood log, to produce a veneeror layer.

During production of the lignocellulose composite products, the pressureapplied to the furnish can depend, at least in part, on the particularcomposite product. For example, the amount of pressure applied in aparticleboard production process can range from about 1 MPa to about 5MPa or from about 2 MPa to about 4 MPa. In another example, the amountof pressure applied in a MDF production process can range from about 2MPa to about 7 MPa or from about 3 MPa to about 6 MPa. The temperaturethe product can be heated to produce an at least partially cured productcan range from a low of about 100° C., about 125° C., about 150° C., orabout 170° C. to a high of about 180° C., about 200° C., about 220° C.,or about 250° C., with suitable ranges including the combination of anytwo values. The length of time the pressure can be applied can rangefrom a low of about 15 second, about 30 seconds, about 1 minute, about 3minutes, about 5 minutes, or about 7 minutes to a high of about 10minutes, about 15 minutes, about 20 minutes, or about 30 minutes, withsuitable ranges including the combination of any two values. Forexample, the length of time the pressure and/or heat can be applied tothe furnish can range from about 30 seconds to about 2 minutes, about 1minute to about 3 minutes, about 1.5 minutes to about 4 minutes, orabout 45 seconds to about 3.5 minutes. The length of time the pressurecan be applied can depend, at least in part, on the particular productand/or the particular dimensions, e.g., thickness of the product.

Wood composite products that can be made using such particulate bindercompositions can include, but are not limited to, oriented strand board(OSB), oriented strand lumber (OSL), medium density fiberboard (MDF),high density fiberboard (HDF), PARALLAM®, plywood, hardboard,waferboard, chipboard, particleboard, flakeboard, and the like. Othercomposite products can be produced from two or more veneer. For example,composite products produced with veneer, in finished form, can includethose products typically referred to as laminated veneer lumber (“LVL”),laminated veneer boards (“LVB”), and/or plywood.

The particulate binder compositions discussed and described herein canbe reconstituted with water or other liquid medium to form a liquidadhesive for making these and other wood composite products. Forexample, the particulate binder compositions can be reconstituted with aliquid medium to have a solids content ranging from a low of about 5 wt%, about 10 wt %, about 15 wt %, or about 20 wt % to a high of about 40wt %, about 50 wt %, about 60 wt %, about 70 wt %, or about 80 wt %,based on the combined weight of the aldehyde based resin, the fillerand/or extender, and the liquid medium, with suitable ranges includingthe combination of any two values.

EXAMPLES

In order to provide a better understanding of the foregoing discussion,the following non-limiting examples are offered. Although the examplesmay be directed to specific embodiments, they are not to be viewed aslimiting the invention in any specific respect. All parts, proportions,and percentages are by weight unless otherwise indicated.

An aqueous phenol-formaldehyde resole resin was used as the aldehydebased resin for all examples. The aqueous phenol-formaldehyde resoleresin had about 44.5 wt % solids, a pH of about 10.0, a viscosity ofabout 160 cP at 25° C., an alkalinity of about 3.5%, and a molar ratioof formaldehyde to phenol of about 2.2:1. Comparative examples CEx. 1and CEx. 2 both used the aqueous phenol-formaldehyde resole resin.

For Examples 1 and 2, ground peanut shells were added to the aqueousphenol-formaldehyde resin as a filler in an amount of about 5 wt % and15 wt %, respectively, based on the solids weight of thephenol-formaldehyde resin. For Example 3, ground peanut shells in anamount of about 10 wt % and corn flour in an amount of about 5 wt %,based on the solids weight of the phenol-formaldehyde resin, were addedto the aqueous phenol-formaldehyde resin as filler and extender,respectively. For example 4, about 5 wt % corn flour, based on thesolids weight of the phenol-formaldehyde resin, was added to the aqueousphenol-formaldehyde resin as an extender. The ground peanut shells usedin Examples 1-3 had an average particle size of about 25.2 μm. The cornflour used in Examples 3 and 4 had an average particle size of about28.6 um, a protein concentration of about 8.5 wt % to about 12.5 wt %,and a moisture concentration of about 7.5 wt % to about 11.5 wt %.

About 8,000 grams of the aqueous phenol-formaldehyde resole resin (CEx.1 and 2) and about 4,000 grams of the aqueous phenol-formaldehyde resoleresin combined with the appropriate amount of filler and/or extender inExamples 1-4 were all spray-dried. The aqueous mixture for each examplehad a solids concentration of about 34 wt %. Each aqueous mixture wasagitated using a high shear mixer that formed a vortex when mixing, thusallowing air to be whipped or blended into the mixture to produce anaerated mixture. The aerated mixture was mixed at room temperature forabout for about 30 seconds, after which the aerated mixture wasimmediately introduced to a spray-drying apparatus. The spray dryingapparatus was a MOBILE MINOR® spray dryer from Niro, Inc. The inlettemperature of the dryer was set at about 160° C. and the feed rate ofthe aerated mixtures were adjusted to yield an outlet temperature ofabout 80° C. to about 85° C. The atomizer speed was set at 5 on thespray dryer's scale of 0 to 10.

The average particle size (μm), packed bulk density (g/cm³), moisturecontent (wt % based on total weight of the spray-dried resin), stroketime (seconds), and fusion diameter (mm) of the spray dried resins forcomparative example CEx. 1 and Examples 1-4 are shown in Table 1 below.The average particle sizes of the powdered resins was determinedaccording to the Structural Board Association (SBA) GPAM2771.3 testprocedure. The packed bulk density of the powdered resins was determinedaccording to the Structural Board Association (SBA) GPAM2771.4 testprocedure. The moisture content of the powdered resins was determinedaccording to the SBA GPAM2771.5 test procedure. The stroke time of thepowdered resins was determined according to the SBA GPAM2771.1 testprocedure. The fusion diameter of the powdered resins was determinedaccording to the SBA GPAM2771.2 test procedure. The packed bulk density,stroke cure, and moisture content for five samples were measured and theaverage of those five tests is shown in Table 1. The fusion diameter fortwo samples was measured and the average of those two tests is shown inTable 1.

The properties of the spray dried resins (CEx. 1 and CEx. 2) and bindercompositions (Ex. 1-4) for the examples are shown below in Table 1.

TABLE 1 Average Size PBD MC SC FD Example Filler Extender (μm) (g/cm3)wt % (sec.) (mm) CEx. 1 0 0 19.2 0.527 3.7 12 28 CEx. 2 0 0 19.2 0.5273.7 12 28 Ex. 1 5 0 17.6 0.532 3.8 12 28 Ex. 2 15 0 15.1 0.53 3.7 12 28Ex. 3 10 5 16.8 0.535 3.5 12 28 Ex. 4 0 5 18.9 0.53 3.6 12 28

Six sets of panels were made, with the six spray-dried resins and bindercompositions discussed above, namely, comparative examples CEx. 1 and 2and inventive examples (Ex. 1-4). Each panel was a single layer,non-oriented, panel. The lignocellulose substrates used to produce allpanels was Southern Yellow Pine having an average flake size of about 3inches and having a moisture concentration of about 5 wt %. Thedifference between comparative examples CEx. 1 and CEx. 2 was the amountof the spray dried resin used to produce the composite products.Comparative example CEx. 1 used 100% loading while comparative exampleCEx. 2 used 95% loading. For the purposes of these examples, 100%percent loading or (% loading) was 1.8 wt %, based on the weight of thedry lignocellulose substrates. As such, the amount of the spray driedresin used in comparative example CEx. 2 was about 1.71 wt %, based onthe weight of the dry lignocellulose substrates. Examples 1-4 all used100% loading, i.e., the mixture of the lignocellulose substrates andparticulate binder composition had a concentration of the bindercomposition of about 1.8 wt %. Slack wax in an amount of about 1 wt %,based on the weight of the lignocellulose substrates was also added. Thepress used to form the panels was a Wabash Metals Hydraulic Press havingpress platens of 24 inches×24 inches. The press heated the panels to atemperature of about 210° C.+/−5.5° C. when the panels were pressed.

Each panel was pressed for a time of about 200 (series of exampleslabeled with an “A”), 220 (series of examples labeled with a “B”), or240 seconds (series of examples labeled with a “C”). For each example,two panels for each of the 200 and 220 second press time were made and 4panels for the 240 second press time were made. The formed panels wereabout 0.4375 inches thick×18 inches×18 inches and had a target densityof 43 pounds per cubic foot (pcf). The internal bond strength for eachexample was measured and determined according to the test procedureprovided for in ASTM D1037-06a. The internal bond strength of 144samples for each example was tested, with the average value for eachexample shown in Table 2 below. Standard statistical methods were usedto derive the data shown in Table 2.

TABLE 2 Means Comparison Press Time, IB, psi IB, psi IB, psi IB, psiExample sec Mean Std. Err. −95% +95% CEx. 1A 200 65.84 2.53 60.75 70.93CEx. 2A 200 32.77 3.8 25.13 40.41 Ex. 1A 200 54.83 2.2 50.4 59.26 Ex. 2A200 60.06 2.68 54.68 65.44 Ex. 3A 200 53.8 2.62 48.53 59.06 Ex. 4A 20057.42 3.36 50.66 64.17 CEx. 1B 220 73.69 2.03 69.6 77.77 CEx. 2B 22042.62 3.91 34.76 50.49 Ex. 1B 220 64.89 2.83 59.19 70.58 Ex. 2B 220 62.92.51 57.84 67.95 Ex. 3B 220 62.19 2.63 56.89 67.49 Ex. 4B 220 79.61 2.3974.8 84.42 CEx. 1C 240 73.9 1.84 70.2 77.59 CEx. 2C 240 67.14 3.17 60.7673.52 Ex. 1C 240 69.93 2.7 64.51 75.36 Ex. 2C 240 74.06 2.82 68.39 79.73Ex. 3C 240 69.15 2.59 63.94 74.37 Ex. 4C 240 71.08 2.78 65.48 76.68

The results of the internal bond strengths for the panels of CEx. 1 and2 and Ex. 1-4 were compared in more detail (Tables 3-5) by usingBayesian methods. Table 3 below, shows the Comparison of Means for theInternal Bond at the 200 second press time.

TABLE 3 Example Mean Diff SD Std. Err. 2.50% Mean 97.50% CEx. 1A 0 2.5370.02534 60.89 65.83 70.88 CEx. 2A −33.12 3.782 0.03219 25.21 32.71 40.19Ex. 1A −11.01 2.194 0.02345 50.5 54.82 59.18 Ex. 2A −5.78 2.669 0.0265354.83 60.05 65.33 Ex. 3A −12.03 2.604 0.02438 48.66 53.8 58.86 Ex. 4A−8.44 3.319 0.0357 50.94 57.39 63.94

Table 4 below, shows the Comparison of Means for the Internal Bond atthe 220 second press time.

TABLE 4 Example Mean Diff SD Std. Err. 2.50% Mean 97.50% CEx. 1B 0 2.0370.02035 69.71 73.68 77.73 CEx. 2B −31.12 3.896 0.03316 34.83 42.56 50.27Ex. 1B −8.81 2.818 0.03013 59.33 64.87 70.47 Ex. 2B −10.79 2.506 0.0249157.99 62.89 67.85 Ex. 3B −11.48 2.62 0.02453 57.02 62.2 67.29 Ex. 4B5.91 2.365 0.02544 74.99 79.59 84.26

Table 3 below, shows the Comparison of Means for the Internal Bond atthe 240 second press time.

TABLE 5 Example Mean Diff SD Std. Err. 2.50% Mean 97.50% CEx. 1C 0 1.8440.01843 70.3 73.89 77.56 CEx. 2C −6.8 3.159 0.02689 60.82 67.09 73.34Ex. 1C −3.97 2.685 0.02871 64.64 69.92 75.25 Ex. 2C 0.16 2.814 0.0279668.55 74.05 79.62 Ex. 3C −4.73 2.579 0.02414 64.07 69.16 74.17 Ex. 4C−2.83 2.752 0.0296 65.71 71.06 76.49

As shown in Tables 2, 3, 4, and/or 5, the internal bond strength for Ex.1A-4A all trended slightly lower than comparative example CEx. 1A. Thecomparative example CEx. 2A that was at only 95% loading yieldedsignificantly lower internal bond strength as compared to comparativeexample CEx. 1A. The internal bond strength for Ex. 1B-3B all trendedslightly lower than comparative example CEx. 1A. The internal bondstrength for Ex. 4B, however, was slightly inside the significancesthreshold and with a trend above that of the comparative example CEx.1B. The comparative example CEx. 2B again yielded significantly lowerinternal bond strength as compared to comparative example CEx. 1B. Theinternal bond strength Ex. 1C, 3C, and 4C all trended slightly lowerthan comparative example CEx. 1C. The internal bond strength for Ex. 2C,however, was slightly inside the significances threshold and with atrend above that of the comparative example CEx. 1C. The comparativeexample CEx. 2C again yielded significantly lower internal bond strengthas compared to comparative example CEx. 1C. The data in Tables 2-5,shows that at the 240 second press time, the binder compositions of Ex.1-4 are all statistically equivalent to the comparative example CEx. 1.

Embodiments of the present invention further relate to any one or moreof the following paragraphs:

1. A binder composition for producing composite lignocellulose products,comprising: an aldehyde based resin; and a filler, an extender, or acombination thereof, wherein the binder composition is in the form ofparticulates, and wherein the particulates each comprises the filler,the extender, or the combination thereof and the aldehyde based resin.

2. A method for producing a binder composition, comprising: combining afiller, an extender, or a both with an aldehyde based resin in thepresence of a liquid medium to produce a mixture; and removing at leasta portion of the liquid medium to produce a particulate bindercomposition, wherein each particulate comprises the filler, theextender, or the combination thereof and the aldehyde based resin.

3. A method for producing a binder composition, comprising: spray-dryingan aerated liquid mixture comprising a filler, an extender, or acombination thereof and an aldehyde based resin to produce a spray-driedbinder composition, wherein the spray-dried binder composition is in theform of particulates, and wherein each particulate comprises the filler,the extender, or the combination thereof and the aldehyde based resin.

4. A composite product, comprising: a plurality of lignocellulosesubstrates and an at least partially cured binder composition, whereinthe binder composition, prior to at least partial curing, comprises: analdehyde based resin; and a filler, an extender, or a combinationthereof, wherein the binder composition is in the form of particulates,and wherein each particulate comprises the filler, the extender, or thecombination thereof and the aldehyde based resin.

5. A method for producing a particulate binder composition, comprising:synthesizing a liquid phenol-formaldehyde resole resin; combining afiller, an extender, or both with the liquid phenol-formaldehyde resoleresin in an amount sufficient to produce a mixture containing about 1 wt% to about 25 wt % of the filler, the extender, or both, based on thecombined weight of the liquid phenol-formaldehyde resole resin solidsand the filler, the extender, or both; agitating the mixture to producean aerated mixture; and spray-drying the aerated mixture to produce aspray-dried particulate binder composition, wherein each particulatecomprises the filler, the extender, or the combination thereof and thealdehyde based resin.

6. A method for making a composite product, comprising: contacting aplurality of lignocellulose substrates with a particulate bindercomposition, the particulate binder composition comprising: an aldehydebased resin; and a filler, an extender, or a combination thereof,wherein each particulate comprises the filler, the extender, or thecombination thereof and the aldehyde based resin; and at least partiallycuring the binder composition to produce a composite product.

7. The binder composition, method, or composite product according to anyone of paragraphs 1 to 6, wherein the particulates have an average sizeranging from about 1 μm to about 150 μm.

8. The binder composition, method, or composite product according to anyone of paragraphs 1 to 7, wherein the particulates have a packed bulkdensity ranging from about 0.15 g/cm³ to about 0.85 g/cm³.

9. The binder composition, method, or composite product according to anyone of paragraphs 1 to 8, wherein the particulates have a liquidconcentration of less than about 10 wt %, based on a total weight of theparticulates.

10. The binder composition, method, or composite product according toany one of paragraphs 1 to 9, wherein the aldehyde based resin comprisesa urea-aldehyde resin, a melamine-aldehyde resin, a phenol-aldehyderesin, a resorcinol-aldehyde resin, a phenol-resorcinol-aldehyde resin,a melamine-urea-aldehyde resin, a phenol-urea-aldehyde resin, or anycombination thereof.

11. The binder composition, method, or composite product according toany one of paragraphs 1 to 10, wherein the aldehyde based resincomprises phenol-formaldehyde resole resin.

12. The binder composition, method, or composite product according toparagraph 11, wherein the phenol-formaldehyde resole resin has aformaldehyde to phenol molar ratio ranging from about 2:1 to about2.65:1.

13. The binder composition, method, or composite product according toparagraph 11 or 12, wherein the liquid phenol-formaldehyde resole resinhas a weight average molecular weight ranging from about 1,000 Daltonsto about 8,000 Daltons.

14. The binder composition, method, or composite product according toany one of paragraphs 1 to 13, wherein the extender is present andcomprises corn flour, soy protein powder, wheat flour, spray driedblood, or any combination thereof.

15. The binder composition, method, or composite product according toparagraph 14, wherein the soy flour comprises soy protein modified withcompounds having the formula R₂NC(═X)NR₂, wherein each R is individuallyselected from the group consisting of H and C₁-C₄ saturated andunsaturated groups, and X is selected from the group consisting of O,NH, and S, soy protein modified with saturated and unsaturated alkalimetal C₈-C₂₂ sulfate and sulfonate salts, or any combination thereof.

16. The binder composition, method, or composite product according toany one of paragraphs 1 to 15, wherein the filler is present andcomprises nut shells, seed shells, fruit pits, animal bones, milwhite,clay, or any combination thereof.

17. The binder composition, method, or composite product according toany one of paragraphs 1 to 16, wherein the filler is present andcomprises wheat shell, corn husk, pecan shell, peanut shell, or anycombination thereof.

18. The binder composition, method, or composite product according toany one of paragraphs 1 to 18, wherein the filler, the extender, or thecombination thereof is present in an amount ranging from about 1 wt % toabout 25 wt %, based on a combined weight of the filler, the extender,or both and the aldehyde based resin.

19. The composite product according to paragraph 4, wherein an amount ofthe aldehyde based resin in the composite product is about 1 wt % toabout 25 wt % less as compared to a comparative composite productproduced with a comparative particulate binder composition having thesame aldehyde based resin but no filler or extender.

20. The composite product according to paragraph 19, wherein an internalbond strength of the composite product is equal to or greater than aninternal bond strength of the comparative composite product.

21. A binder composition for producing composite lignocelluloseproducts, comprising a mixture of a first plurality of particulatescomprising one or more aldehyde based resins and a second plurality ofparticulates comprising one or more fillers, one or more extenders, or acombination thereof.

22. A method for producing a binder composition, comprising: removing atleast a portion of a liquid medium combined with an aldehyde based resinto produce a first plurality of particulates; and combining the firstplurality of particulates with a second plurality of particulates toproduce a binder composition, wherein the second plurality ofparticulates comprises one or more fillers, one or more extenders, or acombination thereof.

23. A method for producing a binder composition, comprising:spray-drying an aerated liquid mixture comprising one or more aldehydebased resins to produce a first plurality of particulates; and combiningthe first plurality of particulates with a second plurality ofparticulates to produce a binder composition, wherein the secondplurality of particulates comprises one or more fillers, one or moreextenders, or a combination thereof.

24. A composite product, comprising: a plurality of lignocellulosesubstrates and an at least partially cured binder composition, whereinthe binder composition, prior to at least partial curing, comprises amixture of a first plurality of particulates comprising one or morealdehyde based resins and a second plurality of particulates comprisingone or more fillers, one or more extenders, or a combination thereof.

25. A method for making a composite product, comprising: contacting aplurality of lignocellulose substrates with a particulate bindercomposition, the particulate binder composition comprising a mixture ofa first plurality of particulates comprising one or more aldehyde basedresins and a second plurality of particulates comprising one or morefillers, one or more extenders, or a combination thereof; and at leastpartially curing the binder composition to produce a composite product.

26. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the first plurality ofparticulates and the second plurality of particulates each have anaverage size ranging from about 1 μm to about 150 μm.

27. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the mixture of the firstplurality of particulates and the second plurality of particulates has apacked bulk density ranging from about 0.15 g/cm³ to about 0.85 g/cm³.

28. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the first plurality ofparticulates has a liquid concentration of less than about 10 wt %,based on a total weight of the first plurality of particulates.

29. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the second plurality ofparticulates has a liquid concentration of less than about 10 wt %,based on a total weight of the second plurality of particulates.

30. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the aldehyde based resincomprises a urea-aldehyde resin, a melamine-aldehyde resin, aphenol-aldehyde resin, a resorcinol-aldehyde resin, aphenol-resorcinol-aldehyde resin, a melamine-urea-aldehyde resin, aphenol-urea-aldehyde resin, or any combination thereof.

31. The binder composition, method, or composite product according toparagraph 30, wherein the aldehyde based resin comprisesphenol-formaldehyde resole resin.

32. The binder composition, method, or composite product according toparagraph 30, wherein the phenol-formaldehyde resole resin has aformaldehyde to phenol molar ratio ranging from about 2:1 to about2.65:1.

33. The binder composition, method, or composite product according toparagraph 30, wherein the liquid phenol-formaldehyde resole resin has aweight average molecular weight ranging from about 1,000 Daltons toabout 8,000 Daltons.

34. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the one or more extenders ispresent and comprises corn flour, soy protein powder, wheat flour, spraydried blood, or any combination thereof.

35. The binder composition, method, or composite product according toparagraph 34, wherein the soy flour comprises soy protein modified withcompounds having the formula R₂NC(═X)NR₂, wherein each R is individuallyselected from the group consisting of H and C₁-C₄ saturated andunsaturated groups, and X is selected from the group consisting of O,NH, and S, soy protein modified with saturated and unsaturated alkalimetal C₈-C₂₂ sulfate and sulfonate salts, or any combination thereof.

36. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the one or more fillers ispresent and comprises nut shells, seed shells, fruit pits, animal bones,milwhite, clay, or any combination thereof.

37. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the one or more fillers ispresent and comprises wheat shell, corn husk, pecan shell, peanut shell,or any combination thereof.

38. The binder composition, method, or composite product according toany one of paragraphs 21 to 25, wherein the one or more fillers, the oneor more extenders, or the combination thereof is present in an amountranging from about 1 wt % to about 25 wt %, based on a combined weightof the first plurality of particulates and the second plurality ofparticulates.

39. The composite product according to paragraphs 24 or 25, wherein anamount of the aldehyde based resin in the composite product is about 1wt % to about 25 wt % less as compared to a comparative compositeproduct produced with a comparative particulate binder compositionhaving the same aldehyde based resin but no filler or extender.

40. The composite product according to paragraph 39, wherein an internalbond strength of the composite product is equal to or greater than aninternal bond strength of the comparative composite product.

41. A method for producing a particulate binder composition, comprising:synthesizing a liquid phenol-formaldehyde resole resin; agitating theliquid phenol-formaldehyde resin to produce an aeratedphenol-formaldehyde resole resin; and spray-drying the aeratedphenol-formaldehyde resole resin to produce a spray-dried particulatephenol-formaldehyde resole resin; and combining the spray-driedparticulate phenol-formaldehyde resole resin with one or more fillers,one or more extenders or a combination thereof to produce a bindercomposition, wherein the one or more fillers, the one or more extenders,or the combination thereof is in particulate form.

Certain embodiments and features have been described using a set ofnumerical upper limits and a set of numerical lower limits. It should beappreciated that ranges from any lower limit to any upper limit arecontemplated unless otherwise indicated. Certain lower limits, upperlimits and ranges appear in one or more claims below. All numericalvalues are “about” or “approximately” the indicated value, and take intoaccount experimental error and variations that would be expected by aperson having ordinary skill in the art.

Various terms have been defined above. To the extent a term used in aclaim is not defined above, it should be given the broadest definitionpersons in the pertinent art have given that term as reflected in atleast one printed publication or issued patent. Furthermore, allpatents, test procedures, and other documents cited in this applicationare fully incorporated by reference to the extent such disclosure is notinconsistent with this application and for all jurisdictions in whichsuch incorporation is permitted.

While the foregoing is directed to embodiments of the present invention,other and further embodiments of the invention may be devised withoutdeparting from the basic scope thereof, and the scope thereof isdetermined by the claims that follow.

What is claimed is:
 1. A binder composition for making a compositelignocellulose product, comprising: a first plurality of particulatescomprising an aldehyde based resin; and about 0.5 wt % to 10 wt % of asecond plurality of particulates, based on a combined weight of thefirst plurality of particulates and the second plurality ofparticulates, the second plurality of particulates having a differentcomposition than the first plurality of particulates and comprising afiller, an extender, or a combination thereof, wherein: the fillercomprises a nut shell, a seed shell, a fruit pit, or any combinationthereof, and the extender comprises corn flour, soy flour, wheat flour,or any combination thereof.
 2. The binder composition of claim 1,wherein the aldehyde based resin comprises a urea-aldehyde resin, amelamine-aldehyde resin, a phenol-aldehyde resin, a resorcinol-aldehyderesin, or any mixture thereof.
 3. The binder composition of claim 1,wherein the aldehyde based resin comprises a phenol-formaldehyde resoleresin.
 4. The binder composition of claim 1, wherein the aldehyde basedresin comprises a phenol-formaldehyde resin having a molar ratio offormaldehyde to phenol of about 2.1:1 to about 2.65:1.
 5. The bindercomposition of claim 1, wherein the first plurality of particulates isfree of the filler and the extender, and wherein the second plurality ofparticulates is free of the aldehyde based resin.
 6. The bindercomposition of claim 1, wherein the binder composition comprises about 1wt % to 9 wt % of the second plurality of particulates, based on thecombined weight of the first plurality of particulates and the secondplurality of particulates.
 7. The binder composition of claim 1, whereinthe second plurality of particulates comprises the filler, and whereinthe filler comprises pecan shell, peanut shell, wheat shell, almondshell, walnut shell, corn husk, or any combination thereof.
 8. Thebinder composition of claim 1, wherein the second plurality ofparticulates comprises the extender, and wherein the extender comprisescorn flour, wheat flour, or a combination thereof.
 9. The bindercomposition of claim 1, wherein the second plurality of particulatescomprises the filler and the extender, and wherein the filler comprisespecan shell, peanut shell, wheat shell, almond shell, walnut shell, cornhusk, or any combination thereof.
 10. The binder composition of claim 1,wherein: the aldehyde based resin comprises a phenol-formaldehyde resinhaving a molar ratio of formaldehyde to phenol of about 2.1:1 to about2.65:1, the filler, if present, comprises pecan shell, peanut shell,wheat shell, almond shell, walnut shell, corn husk, or any combinationthereof, and the extender, if present, comprises corn flour.
 11. Thebinder composition of claim 1, wherein: the binder composition comprisesabout 1 wt % to 9 wt % of the second plurality of particulates, based onthe combined weight of the first plurality of particulates and thesecond plurality of particulates, the aldehyde based resin comprises aphenol-formaldehyde resin having a molar ratio of formaldehyde to phenolof about 1.8:1 to about 2.65:1, and the second plurality of particulatescomprises the filler, wherein the filler comprises pecan shell, peanutshell, or a combination thereof.
 12. A binder composition for making acomposite lignocellulose product, comprising: a first plurality ofparticulates comprising a phenol-formaldehyde resole resin; and about0.5 wt % to about 30 wt % of a second plurality of particulates, basedon a combined weight of the first plurality of particulates and thesecond plurality of particulates, the second plurality of particulateshaving a different composition than the first plurality of particulatesand comprising an extender, wherein the extender comprises corn flour,soy flour, wheat flour, or any combination thereof.
 13. The bindercomposition of claim 12, wherein the extender comprises corn flour. 14.The binder composition of claim 12, wherein the binder compositioncomprises about 1 wt % to about 16 wt % of the second plurality ofparticulates, based on the combined weight of the first plurality ofparticulates and the second plurality of particulates.
 15. The bindercomposition of claim 12, wherein the binder composition comprises about1 wt % to 10 wt % of the second plurality of particulates, based on thecombined weight of the first plurality of particulates and the secondplurality of particulates.
 16. The binder composition of claim 12,wherein the binder composition comprises about 1 wt % to about 16 wt %of the second plurality of particulates, based on the combined weight ofthe first plurality of particulates and the second plurality ofparticulates, and wherein the extender comprises corn flour.
 17. Thebinder composition of claim 12, wherein the second plurality ofparticulates further comprises a filler, and wherein the fillercomprises a nut shell, a seed shell, a fruit pit, or any combinationthereof.
 18. The binder composition of claim 12, wherein the firstplurality of particulates is free of the extender, and wherein thesecond plurality of particulates is free of the phenol-formaldehyderesole resin.
 19. A method for making a composite lignocelluloseproduct, comprising: contacting a plurality of lignocellulose substrateswith a particulate binder composition comprising a first plurality ofparticulates and a second plurality of particulates to produce afurnish, wherein: the binder composition comprises about 0.5 wt % to 10wt % of the second plurality of particulates, based on a combined weightof the first plurality of particulates and the second plurality ofparticulates, the first plurality of particulates comprises an aldehydebased resin, and the second plurality of particulates has a differentcomposition than the first plurality of particulates and comprises afiller, an extender, or a combination thereof, wherein: the fillercomprises a nut shell, a seed shell, a fruit pit, or any combinationthereof, and the extender comprises corn flour, soy flour, wheat flour,or any combination thereof; and at least partially curing the bindercomposition in the furnish to produce a composite lignocelluloseproduct.
 20. The method of claim 19, wherein: the aldehyde based resincomprises a phenol-formaldehyde resin having a molar ratio offormaldehyde to phenol of about 1.8:1 to about 2.65:1, the secondplurality of particulates comprises the filler and the filler comprisespecan shell, peanut shell, wheat shell, almond shell, walnut shell, cornhusk, or any combination thereof, and the composite lignocelluloseproduct is a particleboard, a fiberboard, a plywood, an oriented strandboard, or a laminated veneer board.
 21. The method of claim 19, wherein:the binder composition comprises about 1 wt % to 9 wt % of the secondplurality of particulates, based on the combined weight of the firstplurality of particulates and the second plurality of particulates, thealdehyde based resin comprises a phenol-formaldehyde resin having amolar ratio of formaldehyde to phenol of about 2.1:1 to about 2.65:1,the filler, if present, comprises pecan shell, peanut shell, wheatshell, almond shell, walnut shell, corn husk, or any combinationthereof, and the extender, if present, comprises corn flour.
 22. Themethod of claim 19, wherein the first plurality of particulates is freeof the extender, and wherein the second plurality of particulates isfree of the phenol-formaldehyde resole resin.